Spectroscopic and Computational Studies of an End-on Bound Superoxo-Cu(II) 
Complex: Geometric and Electronic Factors That Determine the Ground State

Woertink, Julia S.; Tian, Li; Maiti, Debabrata; Lucas, Heather R.; Himes, Richard A.; Karlin, Kenneth D.; Neese, Frank; Würtele, Christian; Holthausen, Max C.; Bill, Eckhard; Sundermeyer, Jörg; Schindler, Siegfried; Solomon, Edward I.

doi:10.1021/ic101138u

Datensatz

DATENSATZ AKTIONENEXPORT

Zur Ablage hinzufügen

Lokale TagsFreigabegeschichteDetailsÜbersicht

Freigegeben

Zeitschriftenartikel

Spectroscopic and Computational Studies of an End-on Bound Superoxo-Cu(II) Complex: Geometric and Electronic Factors That Determine the Ground State

MPG-Autoren

/persons/resource/persons137604

Bill, Eckhard
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

Externe Ressourcen

Es sind keine externen Ressourcen hinterlegt

Volltexte (beschränkter Zugriff)

Für Ihren IP-Bereich sind aktuell keine Volltexte freigegeben.

Volltexte (frei zugänglich)

Es sind keine frei zugänglichen Volltexte in PuRe verfügbar

Ergänzendes Material (frei zugänglich)

Es sind keine frei zugänglichen Ergänzenden Materialien verfügbar

Zitation

Woertink, J. S., Tian, L., Maiti, D., Lucas, H. R., Himes, R. A., Karlin, K. D., et al. (2010). Spectroscopic and Computational Studies of an End-on Bound Superoxo-Cu(II) Complex: Geometric and Electronic Factors That Determine the Ground State. Inorganic Chemistry, 49(20), 9450-9459. doi:10.1021/ic101138u.

Zitierlink: https://hdl.handle.net/21.11116/0000-0008-0FBF-2

Zusammenfassung

A variety of techniques including absorption, magnetic circular dichroism (MCD), variable-temperature, variable-field MCD (VTVH-MCD), and resonance Raman (rR) spectroscopies are combined with density functional theory (DFT) calculations to elucidate the electronic structure of the end-on (η¹) bound superoxo-Cu(II) complex [TMG₃trenCuO₂]⁺ (where TMG₃tren is 1,1,1-tris[2-[N²-(1,1,3,3-tetramethylguanidino)]ethyl]amine). The spectral features of [TMG₃trenCuO₂]⁺ are assigned, including the first definitive assignment of a superoxo intraligand transition in a metal-superoxo complex, and a detailed description of end-on superoxo-Cu(II) bonding is developed. The lack of overlap between the two magnetic orbitals of [TMG₃trenCuO₂]⁺ eliminates antiferromagnetic coupling between the copper(II) and the superoxide, while the significant superoxo π*σ character of the copper d_z² orbital leads to its ferromagnetically coupled, triplet, ground state.